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GENERAL PHYSICS II Electromagnetism & Thermal Physics 4/29/2008 Chapter XV The First Law of Thermodynamics §1 Heat, work and paths of a thermodynamic process §2 The first law of thermodynamics §3 Kinds of thermodynamic processes §4 Thermodynamic processes for an ideal gas 4/29/2008 We knew that the concepts of mechanical work and energy play an important role in studying mechanical phenomena Concerning to thermal phenomena, there exits a new form of energy called “heat”: Heat can be transferred from one to other systems For a system with volume held constant, the effect of heat is to change the temparature of a system In general cases, for a system there exist, at the same time, transfer or exchange of heat and mechanical work → the GOAL of thermodynamics is the study of the relationships involving heat, mechanical work, the laws that govern energy transfers 4/29/2008 §1 Thermodynamic systems and processes: 1.1 Thermodynamic systems, heat and work: In any study of heat, work transfer we must define exactly what are the objects under consideration: A thermodynamic system is any collection of objects that is regarded as a unit and that may have the potential to exchange energy with other bodies beside the system All the other bodies which have energy exchanges with the considered system are called surroundings or environment 4/29/2008 Then we must fix the convention on the symbol for heat and work: surroundings system We will always denote by Q the quantity of heat added to the system by W the mechanical work done by the system Therefore Q and W are understood as algebraic values, they can be positive, negative or zero Q>0 surroundings system surroundings system W>0 Work is done by the system 4/29/2008 surroundings Q , and when the gas is compressed, V2 < V1 → Wby < (it means that the surroundings does work on the gas) In a p-V diagram, the equilibrium intermediate states are represented by the points on a curve, and the work is represented as the area under the curve p V1 4/29/2008 V2 V 1.3 Paths between thermodynamic states: When a thermodynamic system changes from an initial state to a final state, it passes through a series of (equilibrium) intermediate states However, with the same initial and final states, the system can pass in very different ways On a P-V diagram, every way corresponds to a curve which is called the path between thermodynamic states Examples: Two different paths between the states and : p p 1 p1 p1 p2 V V2 → : keep the pressure constant at p1 while the gas expands to the volume V → : reduce the pressure to p2 at constant volume V2 4/29/2008 p2 V V1 → 4: reduce the pressure at the constant volume V1 → 2: keep the pressure constant at p2 while the gas expands to the volume V2 It is important to remark that with the same intial and final states: The work done by the system depends on the intermediate states, that is, on the path, Like work, the heat which the system exchanges with the surroundings depends also on the path Examples: p p 2 V In an isothermal expansion of the gas we must supply an input heat to keep constant temperature 4/29/2008 V Gas can expand in an container which is isolated from surroundings (no heat input) §2 The first law of thermodynamics: 2.1 Internal energy of a system: The internal energy of a system is the energy that the system owns We can define: Internal energy = ∑kinetic energies of constituent particles + ∑potential energies between them (Note that the internal energy does not include potential energy arising from the interaction between the system and its surroundings, for example, system and gravitaitonal field) For an ideal gas we know how can calculate the internal energy But for any real system, the calculation of the internal energies by this way would be very complicated 4/29/2008 10 §3 Kinds of thermodynamic processes: We know that there are many different paths between thermodynamic states We will study four specific kinds of thermodynamic processes which are important in practical applications 3.1 Adiabatic process: Definition: Adiabatic process is defined as one with no heat transfer into or out of a system, Q = V Examples: Gas in a container which is surrounded by a thermally isolating material A expansion (or compression) of gas which takes place so quickly that there is not enough time for heat transfer From the 1st law: Δ = U2 – U1 = - W U (adiabatic process) p 4/29/2008 13 3.2 Isochoric process: Definition: This is a constant-volume process Example: A gas in a closed constant-volume container p When the volume of a thermodynamic system is constant, it does no work on its surroundings V W=0 From the 1st law: Δ = U2 – U1 = Q U (isochoric process) Since the system does no work → all the energy (heat) added remains in the system → the iternal energy increases 4/29/2008 14 3.3 Isobaric process: Definition: This is a constant-pressure process In a isobaric process, none of three quantities Δ Q, W is zero U, p V Work done by the system is easily calculated: W = p (V2 – V1 ) 4/29/2008 15 3.4 Isothermal process: Definition: This is a constant-temperature process p To keep temprature constant, the system must exchange heat with the surroundings, and the exchange must be slowly that thermal equilibrium is maintained V In general, in a isothermal process, none of Δ Q, W is zero U, Only in the case of an ideal gas, the internal energy U ~ T → Δ = in a isothermal process U 4/29/2008 16 §4 Thermodynamic processes for an ideal gas: In this section, by applying the 1st law of thermodynamics we study in more details thermodynamic processes for an ideal gas For an ideal gas, with the help of kinetic-molecular model, we know that the internal energy of an ideal gas depends only on its temperature, not on its pressure or volume Owing to the explicit relation between the internal energy U and temperature T we can find explicit equations which relate heat, work and internal energy 4/29/2008 17 4.1 Constant-volume and constant-pressure heat capacities of an ideal gas: We knew the concept of heat capacity of an ideal gas in a constant-volume process Now consider more general cases of thermodynamic process The general definition of heat capacity is the following equation: where Δ is the quantity of heat added to the system for increase Q Δ in temperature T This definition can give rise different heat capacities which depend on the paths of thermodynamic process 4/29/2008 18 The constant-volume heat capacity is defined by Notes: Here we replace Δ by Δ because no work done in the process Q U If we understand CV as molar constant-volume heat capacity, then Δ is the heat added per mole Q The constant-pressure heat capacity: For a constant-pressure process the effect of the heat added to the system is twofold: to increase the internal energy and to work 4/29/2008 19 • Applying the 1st law we can write • At the limit Δ → : T • In the case of an ideal gas, U depends only on T , we have • Using the equation of state of an ideal gas we obtain the relation for the molar heat capacities CP and CV : CP = CV + R (See experimantal values of CV and CP given in textbook, p 740, tab 19.1) 4/29/2008 20 4.2 Isothermal processes for an ideal gas: For a fix amount of ideal gas, from the state equation thermal processes are represented by P-V curves shown in the picture These curves are called isotherms Calculate the work done by the gas in the isothermal expansion A → B with a fixed temperature T = T0 (see the picture): where K = n R, n is the number of moles 4/29/2008 21 For the case of an ideal, the internal energy U depends only on temperature → Δ = in isothermal processes By the st law, U the heat added to the gas for keeping constant temperature equals to the work done by the gas: Q = W 4.3 Adiabatic processes for an ideal gas: According to the definition, in an adiabatic process no heat transfer takes place → Q = Remember for an ideal gas, U depends only on temperature T , and → for an adiabatic expansion (or compression) of gas, from 1st law we have Q = Δ + P Δ = CV Δ + P Δ = U V T V 4/29/2008 22 For n moles of ideal gas n CV Δ = - P Δ = - n(RT/V) Δ T V V apply the state equation for n moles of ideal gas For an infinitesimal process we have R CP V CP C 1 CV CV CV dT dV 1) ( T V 4/29/2008 dT R dV T CV V C P where CV (the ratio of heat capacities) (γ is always positive ! -1) 23 By integrating we obtain ln T 1) ln V ( constant ln(TV 1 ) constant ln T V ln constant TV constant It means that for an adiabatic process from a initial state (T1, V1) to a final state (T2, V2) : T V V 1 T 1 2 We can convert the relation for (T, V) into a relation for (p, V) PV nR by substituting T PV V constant nR PV constant It means that for an adiabatic process: 4/29/2008 P1V1 P2V 2 24 Calculate the work done by the gas From the 1st law: W nCV (T2 ) V (T1 ) U T nC T Using PV = n RT we have C W V ( PV1 2V2 ) P ( PV1 2V2 ) P 1 R 1 P-V curves for adiabatic processes are shown in the picture, together with isoterms for comparison Remark: Adiabatic curves are more sloping than isoterms (Compare PV constant with PV constant ) An adiabatic expansion (for example A → D) causes a drop in temperature (T → T1) 4/29/2008 • Adiabatic curves: blue dashed • Isoterms: solid black 25 Summary Δ = Q-W U The first law of thermodynamics: The change of internal energy The work done by a system: The quantity of heat added to the system The work done by the system V2 W PdV V1 The relation between heat capacities: CP = CV + R CP CV 4/29/2008 26 For an isothermal process of an ideal gas: Δ =0 U V Q nRT0 ln W V 1 For an adiabatic process of an ideal gas: TV constant PV constant C W V (T1 ) V (PV1 2V2 ) nC T P (PV1 2V2 ) P 1 R 1 4/29/2008 27 .. .Chapter XV The First Law of Thermodynamics §1 Heat, work and paths of a thermodynamic process §2 The first law of thermodynamics §3 Kinds of thermodynamic processes §4 Thermodynamic... Having the concept of the internal energy, we can formulate the first law of thermodynamics 4/29/2008 11 2.2 Formulation of the first law of thermodynamics: Consider a change of state of the system... Q-W U The first law of thermodynamics: The change of internal energy The work done by a system: The quantity of heat added to the system The work done by the system V2 W PdV V1 The relation